Process for the production of amino



United States Patent 26,069 PROCESS FOR THE PRODUCTION OF AMINO HYDROXYETHERS John A. Frump, Vigo, Ind., assignor to Commercial Solvents Corporation, New York, N.Y., a corporation of Maryland No Drawing. Original No. 3,179,697, dated Apr. 20,

1965, Ser. No. 27,468, May 9, 1960. Application for reissue Dec. 28, 1965, Ser. No. 523,830

17 Claims. (Cl. 260-570.6)

Matter enclosed in heavy brackets appears in the original patent but forms no part of this reissue specification; matter printed in italics indicates the additions made by reissue.

My invention relates to a process for producing amino hydroxyethers, and more particularly it relates to a process for producing amino hydroxyethers having the following general formula:

R R A]J(CIIRQ)J"RJ N'IB wherein R is a member selected from the group consisting of methyl and hydrogen and wherein R is a member selected from the group consisting of lower alkyl, lower hydroxyalkyl and a radical having the formula:

wherein R is a member selected from the group consisting of the radicals:

and

l 0 H 11 N11,

wherein R is a member selected from the group consisting of hydrogen, phenyl, amino substituted phenyl, halo substituted phenyl, alkyl, hydroxyl substituted alkyl, halo substituted alkyl, alkenyl, and phenyl substituted alkyl, wherein x is an integer ranging from 1 to and y is an integer ranging from from 1 to 20.

The above-described amino hydroxyethers and a process for their preparation are described and claimed in my co-pending application, U.S. Serial No. 8,234, now abandoned. According to the process of Serial No. 8,234, now abandoned, the amino hydroxyethers are prepared by hydrogenating the corresponding nitro hydroxy others. The nitro hydroxyethers which thus serve as intermediates in producing the amino hydroxyethers are prepared by oxyalkylating a nitro alcohol having the following general formula:

11 l [it-('J-(ti in) xo [1] i N O 1 Reissued Aug. 2, 1966 ice wherein R is a member selected from the group consisting of lower alkyl radicals and lower hydroxyalky] radicals with a compound containing at least one grouping in the presence of boron trifluoride and R has the ab0ve-described meaning.

The process of my co-pending application U.S. Serial No. 8,234, now abandoned while being a relatively efficien-t method for producing amino hydroxyethers, is subject to certain inherent disadvantages. For example, the time required for complete hydrogenation of the nitro hydroxycther is quite long. The yield of the intermediate nitro hydroxyether is relatively low and the many reaction steps are cumbersome and difiicult to adapt to industrial production.

Previously it has been observed that addition products of epoxides and amino alcohols give secondary and tertiary amine adducts instead of the desired amino hydroxyethers thereby necessitating the utilization of the corresponding nitro compounds as intermediates.

1 have now discovered a method for producing amino hydroxyethers having the following general formula:

'5 RC(CI R )rRt wherein R is a member selected from the group consisting of methyl and hydrogen and wherein R is a member selected from the group consisting of lower alkyl, lower hydroxy alkyl and a radical having the formula:

wherein R is a member selected from the group consisting of the radicals:

-[0crIioIr],-Ou

wherein R is a member selected from the group consisting of hydrogen, phenyl, amino substituted phenyl, halo substituted phenyl, alkyl, hydroxyl substituted alkyl, halo substituted alkyl, alkenyl and phenyl substituted alkyl, wherein x is an integer ranging from 1 to 20 and y is an integer ranging from 1 to 20 directly from amino alcohols having the following general formula:

wherein R is a member selected from the group consisting of methyl and hydrogen,- wherein R is a member selected from the group consisting of lower alkyl radicals and lower hydroxyalkyl radicals without first producing the intermediate nitro hydroxyether. My new process is not only economical in allowing the utilization of cheap, available raw materials and convenient easily operated apparatus but is advantageous in its production of high conversions and good yields of amino hydroxyethers.

My new process for producing the above-mentioned amino hydroxyethers consists essentially of first reacting an amino alcohol having the following general formula:

wherein R is a member selected from the group consisting of methyl and hydrogen; wherein R is a member selected-from the group consisting of lower alkyl radicals and lower hydroxyalkyl radicals with sodium in an amount sulficient to provide 1 mol of sodium for each hydroxyl group of the aminoalcohol to be oxyalkylated, oxyalkylating the thus treated amino alcohol with a compound containing at least one o C C groupingto form an amino oxyalkylation product, treating the amino oxyalkylation product with water and carbon dioxide and recovering the thus produced amino hydroxyether.

Examples of amino alcohols used to prepare my compounds include Z-amino-Z-methyl-l-propanol, 3-amino-3-methyl2-butanol,

tris hydroxymethyl aminomethane, Z-amino-Z-propyl-l-propanol, 2-amino-2-methyl-l-octanol, Z-amino-Z-propyl-1-tridecanol[,] and 2-amino-2-ethyl-1-nonadecanol[, etc., and the like] The epoxides from which I prepare my compounds must contain at least one grouping. Representative epoxides include alkylene oxides such as ethylene oxide, butene-l-oxide, isobutylene oxide, butadiene monoxide, 1,2-epoxyoctane, 1,2-epoxytetradecane, 1,2-epoxynonadecane, etc.; alkylene dioxides such as butadiene dioxide, etc.; halo substituted alkylene oxides such as chloropropylene oxide, hromopropylene oxide, etc.; phenyl substituted alkylene oxides such as 1.2 epoxyethylbenzene, 1,2 epoxyoctylbenzene, 1,2- cpoxyheptadecylbenzene, etc.; aminophenyl substituted alkylene oxides such as 1.2-epoxyethylaminobenzene, etc.; halophenyl substituted alkylene oxides such as 1,2-epoxychlorobcnzene[, etc., and the like].

In carrying out my invention I add sodium preferably in the form of sodium sand or sodium methoxide to the amino alcohol preferably at a temperature ranging from about 50 C. to about 100 C. Then the thus treated amino alcohols are oxyalkylated using an epoxide at temperatures ranging from about to about 150 C. to form an amino oxyalkylation product, the amino oxyalkylation product is then treated with water and carbon dioxide to form the amino hydroxyether and the thus formed amino hydroxyether is then recovered from the reaction mixture.

While the broad temperature range of from about 0 to about 150 C. and the broad pressure range of about atmospheric to about 20 p.s.i.g. is suitable for the oxyalkylation step of my reaction, I prefer to use temperatures ranging from about C. to about C. and pressures ranging from about 1 to about 5 p.s.i.g. When temperatures below the melting point of the amino alcohol used in my invention are utilized I prefer to use a solvent for the amino alcohol inert to the reactants and the reaction product. Example of such solvents which are useful in my invention are xylene, carbon tetrachloride and dioxane[, etc., and the like].

The molecular portions used in the oxyalkylating step of my invention can vary considerably depending on the amino alcohol and epoxidc used and/or on the final product desired. Ordinarily, molar ratios of amino alcohol to cpoxide of not less than 1 to 1 and not more than 1 to 20 respectively are useful in my process.

In carrying out the CO step of my process I can first add water to the sodium treated amino alcohol to form a mixture and then add CO to the mixture to produce the amino hydroxyether of my invention.

The amino hydroxyethers produced by the process of my invention can then be recovered by any suitable means such as distillation.

While I do not wish to be limited to any particular theory as to the reaction mechanism for my invention, I believe the explanation for the success of my process, which permits formation of amino hydroxyethers without utilization as intermediates of the corresponding nitro hydroxycthers, lies in the following example wherein the amino alcohol, 2-amino-2-mcthyl-l-propanol, and the epoxy compound, ethylene oxide, are used as illustrative compounds:

It is theorized from the above reaction mechanism that at least one mole of sodium is needed for each mole of amino alcohol having one hydroxy group to prevent addition to the amine during the oxyalkylation step. Therefore, when amino diols are utilized, two moles of sodium for every mole of amino diol will be needed; and when amino triols are utilized, three moles of sodium for every mole of amino triol will be needed.

The following examples are offered to illustrate my invention; however, I do not intend to be limited to the specific materials, proportions and procedures shown. Rather, I intend for equivalents obvious to those skilled in the art to be included within the scope of my invention.

EXAMPLE I To a [l] 2 liter flask containing 630 grams of Z-amino- 2-methyl-l-propanol were slowly added 161 grams of sodium sand in xylene with accompanying agitation to form a uniform mixture. To the thus formed mixture were then added 300 milliliters of xylene. Ethylene oxide was added at atmospheric pressure and at room temperature for about 4 hours. At the end of the ethylene oxide addition, 126 grams of water were added to the mixture followed by the addition of 276 grams of carbon dioxide. After the carbon dioxide addition, the reaction product was allowed to stand for one hour. After the one-hour period, the reaction mixture was withdrawn from the container and Na CO and other impurities were re moved by filtration. The xylene and water were then separated from the reaction mixture by fractional distillation. The residue thus obtained was subjected to fractional distillation under vacuum. 2-methyl-6-hydroxy-4- oxa-2-hexylamine in the amount of 118.5 grams was collected.

The following data were determined for the compound:

Found, percent Calculated, percent N 11 c N i H 0 10.51 11.17 53.45 10.5 l 11.3 541i EXAMPLE II Z-amino-Z-methyl-l-propanol and 1,2-epoxyethylbenzene were reacted by the process described in Example I to produce 2-n1ethyl-9-hydroxy-4,7-diaxo 6,9-diphenyl-2- nonylamine.

EXAMPLE III 2-amino-2-methyl-l-propanol and 1,2-epoxyheptadecane were reacted following the procedure of Example I to give 2 methyl 9 hydroxy 4,7 dioxa 6,9 dipentadecyl-2-nonylamine.

EXAMPLE V 2 amino 2 methyl 1 propanol and chloropropylene oxide were reacted following the procedure of Example I to give 2-methyl-6hydroxy-4-oxa-6-chloromethyl-Z-hexylamine.

EXAMPLE VI 2-amino-2-methyl-l-propanol and 1,2-epoxyheptadecylbenzene were reacted following the procedure of Example I to give 2 methyl 9 hydroxy 4,7 dioxide- 6,9-dipentadecylphenyl-Z-nonylamine.

EXAMPLE VII Z-amino-Z-methyl-l-propanol and butadiene dioxide were reacted following the procedure of Example I to give 2,11 dimethyl 6,7 dihydroxy 4,9 dioxa 2,11- [decane] dodecane-diamine.

EXAMPLE VIII 2-amino-2-methyl-l-propanol and propylene oxide were reacted following the procedure of Example I to give 2 methyl 9 hydroxy 4,7 dioxa 6,9 dimethyl-2-nonylamine.

EXAMPLE IX 3-methyl-3-amino-2 butanol were reacted with ethylene oxide following the procedure of Example I to give 2,3-dimethyl-6hydroxy-4-oxa-2-hexylamine.

EXAMPLE X 2-amino-2-methyl-l-hexanol and ethylene oxide were reacted following the procedure of Example I to give [2 amino 2 methyl 9 hydroxy 6 oxa 2 nonyl amine] S-methyl-l-hydroxy-3-0.ra-5-n0nyfamine.

6 EXAMPLE x1 Tris(hydroxymethyl)aminomethane and ethylene oxide were reacted following the procedure of Example I to give tris(Z-hydroxyepoxymethyl)methylamine.

Now having described my invention, what I claim is:

l. A process for the production of a compound having the following general formula:

R R-C '(CIIRl)z-R:

NH. wherein R is a member selected from the group consisting of methyl and hydrogen; wherein R is a member selected from the group consisting of lower alkyl, lower hydroxyalkyl and a radical having the formula:

wherein R is a member selected from the group consisting of the radicals:

-[OCIIz-(]1Il],0l1

wherein R is a member selected from the group consisting of hydrogen, phenyl, amino substituted phenyl, halo substituted phenyl, alkyl, hydroxyl substituted alkyl, halo substituted alkyl, alkenyl and phenyl, substituted alkyl, wherein x is an integer ranging from 1 to 20 and y is an integer ranging from 1 to 20 which comprises interacting an amino alcohol having the following general formula:

Nrr,

wherein R is a member selected from the group cons/sh ing of methyl and hydrogen; wherein R is a member selected from the group consisting of lower alkyl and lower hydroxy alkyl, with sodium in an amount sufficient to provide 1 mol of sodium for each hydroxyl group of the amino alcohol to be oxyalkylated, oxyalkylating the resulting amino-ONa compound with a compound containing at least one grouping selected from the group consisting of alkylene oxides, halo substituted alkylene oxides, phenyl substituted alkylene oxides, aminophenyl substituted alkylene oxides, halo phenyl substituted alkylene oxides, and alkylene dioxides, at temperatures ranging from about 0 to about C. and at pressures ranging from atmospheric to 20 p.s.i.g. to form an amino sodium-containing oxyalkylation product, subsequently treating the amino sodium-containing oxyalkylation product with water and carbon dioxide and recovering the thus produced amino hydroxyether.

2. The process of claim 1 wherein the temperature ranges from about 90 C. to about 130 C. and the pressure ranges from about 1 to about p.s.i.g.

3. The process of claim 1 wherein the reaction is carried out in the presence of a solvent inert to the reactants and the reaction products.

4. A process for the production of 2-methyl-9-hydroxy- 4,7-dioxa-6,9-dipheny1-2-nonylamine which comprises interacting 2-amino-2-methyl-l-propanol with sodium in an amount sufiicient to provide 1 mol of sodium for each hydroxyl group of the amino alcohol to be oxyalkylated, oxyalkylating the resulting arnino-ONa compound with 1,2-epoxyethylbenzene at temperatures ranging from about 0 to about 150 C. and at pressures ranging from atmospheric to 20 p.s.i.g. to form an amino sodium-containing oxyalkylation product, and subsequently treating the amino sodium-containing oxyalkylation product with water and carbon dioxide and recovering the thus produced aminohydroxy ether compound.

5. A process for the production of 2-methy1-6-hydroxy- 4-oxa-2-hexylamine which comprises interacting 2-amino- 2-methyl-l-propanol with sodium in an amount sufficient to provide 1 mol of sodium for each hydroxyl group of the amino alcohol to be oxyalkylated, oxyalkylating the resulting amino-ONa compound with ethylene oxide at temperatures ranging from about 0 to 150 C. and at pressures ranging from atmospheric to 20 p.s.i.g. to form an amino sodium-containing oxyalkylation product, subsequently treating the amino-sodium-containing oxyalkylation product with water and carbon dioxide and recovering the thus produced aminohydroxy ether compound.

6. A process for the production of 2-methyl-6-hydroxy- 4oxa-6-hexylphenyl-2-hexylamine which comprises interacting 2-amino-2-methyl-l-propanol with sodium in an amount sufiicient to provide 1 mol of sodium for each hydroxyl group of the amino alcohol to be oxyalkylated, oxyalkylating the resulting amino-ONa compound with 1.2 epoxyoctylbenzene at temperatures ranging from about 0 to about 150 C. and at pressures ranging from about atmospheric to about 20 p.s.i.g. to form an amino sodium-containing oxyalkylation product, subsequently treating the amino sodium-containing [oxylakylation] onalkyiation product with water and carbon dioxide and recovering the thus produced amino hydroxyether compound.

7. A process for the production of 2-methyl-9-hydroxy 4.7 dioxa 6,9 dipentadecyl 2 nonylamine which comprises interacting 2-amino-2-methyl-1-propanol with sodium in an amount sufiicinet to provide 1 mol of sodium for each hydroxy group of the amino alcohol to be oxyalkylated, oxyalkylating the resulting amino-ONa compound with 1,2-epoxyh6ptadecane at temperatures ranging from about 0 to 150 C. and at pressures ranging from about atmospheric to about 20 p.s.i.g. to form an amino sodiumcontaining oxyalkylation product, subsequently treating the amino sodium-containing [oxylakylation] oxyulkylation product with water and carbon dioxide and recovering the thus produced amino hydroxyether compound.

8. A process for the production of 2-methyl-6-hydroxy-4-oxa-6-chloromethyI-Z-hexylamine which comprises interacting 2amino-2-methyl-l-propanol with sodium in an amount sufficient to provide 1 mol of sodium for each hydroxyl group of amino alcohol to be oxyalkylated, oxyalkylating the resulting amino-ONa compound with chloropropylene oxide at temperatures ranging from about 0 to about 150 C. and at pressures ranging from about atmospheric to about 20 p.s.i.g. to form an amino sodium-containing oxyalkylation product, subsequently treating the amino sodium-containing oxyalkylation product with water and carbon dioxide and recovering the thus produced amino hydroxyether compound.

9. A process for the production of 2-methyl-9-hydroxy 4,7 dioxa 6,9 dipentadecylphenyl 2 nonylamine which comprises interacting 2-amino-2-methy1-1- propanol with sodium in an amount sufficient to provide 1 mo] of sodium for each hydroxyl group of the amino alcohol to be oxyalkylated, oxyalkylating the resulting amino-ONa compound with 1,2epoxyheptadecylbenzene at temperatures ranging from about 0 to about C. and at pressures ranging from atmospheric to 20 p.s.i.g. to form an amino sodium-containing oxyalkylation product, subsequently treating the amino sodium-containing oxyalkylation product with water and carbon dioxide and recovering the thus produced amino hydroxyether compound.

10. A process for the production of 2,11-dimethyl-6,7- dihydroxy 4.9 dioxa 2,ll-[dceanediamine] dodecmtedimnirte which comprises interacting 2-amino-2- methyl-1-propanol with sodium in an amount sufficient to provide 1 mol of sodium for each hydroxyl group of the amino alcohol to be oxyalkylated, oxyalkylating the resulting amino-ONa compound with butadiene dioxide at temperatures ranging from about 0 to about 150 C. and at pressures ranging from about atmospheric to about 20 p.s.i.g. to form an amino sodium-containing oxyalkylation product, subsequently treating the amino sodium-containing oxyalkylation product with water and carbon dioxide and recovering the thus produced amino hydroxyether compound.

11. A process for the production of 2-methyl-9- hydroxy-4,7-dioxa-6,9-dimethyI-Z-nonylamine which comprises interacting 2-amino-2-methyl-l-propanol with sodium in an amount sulficient to provide 1 mol of sodium for each hydroxyl group of the amino alcohol to be oxalkylated, oxyalkylating the resulting amino-ONa compound with propylene oxide at temperatures ranging from about 0 to about 150 C. and at pressures ranging from about atmospheric to about 20 p.s.i.g. to form an amino sodium-containing oxyalkylation product, subsequently treating the amino sodium-containing oxyalkylation product with water and carbon dioxide and recovering the thus produced amino hydroxyether compound.

12. A process for the production of 2,3-dimethyl-6- hydroxy-4-oxa-Z-hexylamine which comprises interacting 3-methyl-3-amino-2-butanol with sodium in an amount sufiicient to provide 1 mol of sodium for each hydroxyl group of the amino alcohol to be oxyalkylated, oxyalkylating the resulting amino-ONa compound with ethylene oxide at temperatures ranging from about 0 to about 150 C. and at pressures ranging from about atmOspheric to about 20 p.s.i.g. to form an amino sodiumcontaining oxyalkylation product, subsequently treating the amino sodium-containing oxyalkylation product with water and carbon dioxide and recovering the thus produced amino hydroxyether compound.

13. A process for the production of [2-amino-2- methyl 9 hydroxy 6 oxa 2 nonylamine] 5-methyl- 1-hydr0xy-3-oxa-5-nonylamine which comprises interact ing 2 amino 2 methyl 1 hexanol with sodium in an amount sufiicient to provide 1 mol of sodium for each hydroxyl group of the amino alcohol to be oxyalkylated, oxyalkylating the resulting amino-ONa compound with ethylene oxide at temperatures ranging from about 0 to about 150 C. and at pressures ranging from about atmospheric to about 20 p.s.i.g. to form an amino sodium-containing oxyalkylation product, subsequently treating the amino sodium-containing oxyalkylation product with water and carbon dioxide and recovering the thus produced amino hydroxyether compound.

14. A process for the production of [2 amino 2- methyl 19 oxa 21 hydroxy 2 heneicosylamine] 5 methyl I hydroxy 3 oxa 5 docosamine which comprises interacting 2-amino-2-methyl-l-nonadecanol with sodium in an amount sufficient to provide 1 mol of sodium for each hydroxyl group of the amino alcohol to be oxyalkylated, oxyalkylating the resulting amino- ONa compound with ethylene oxide at temperatures ranging from about to about 150 C. and at pressures ranging from about atmospheric to about 20 p.s.i.g. to form an amino-sodium-containing oxyalkylation product, subsequently treating the amino-sodium-containing oxyalkylation product with water and carbon dioxide and recovering the thus produced amino hydroxyether compound.

15. A process for the production of tris(2-hydroxyepoxymethyl)methylam ine which comprises interacting tris(hydroxymethyl)aminomethane with sodium [an] in an amount sufiicient to provide 1 mol of sodium for each hydroxyl group of the amino alcohol to be oxyalkylated, oxyalkylating the resulting amino-ONa compound with ethylene oxide at temperatures ranging from about 0 to about 150 C. and at pressures ranging from about atmospheric to about 20 p.s.i.g. to form an amino sodium-containing oxyalkylation product, subsequently treating the amino sodium-containing oxyalkylation product with water and carbon dioxide and recovering the thus produced amino hydroxyether compound.

16. A process for the production of a compound having the following general formula:

f RC(GHRO,R:

wherein R is a member selected from the group consisting of methyl and hydrogen; whereIn R is a member selected from the group consisting of lower a kyl, lower hydroxyalkyl and a radical having the formula:

[( Z)X J wherein R is a member selected from the group consisting of the radicals:

-[O-Cllz(Jli],Oll

and

wherein R is a member selected from the group consisting of hydrogen, phenyl, amino substituted phenyl, halo substituted phenyl, alkyl, hydroxyl substituted alkyl, halo substituted alkyl, alkenyl and phenyl substituted alkyl, wherein X is an integer ranging from 1 to 20 and y is an integer ranging from 1 to 20 which comprises interacting an amino alcohol having the following general formula:

s [R;( J(Clh),OH]

IL'II:

11?: RyC-(C'IIRJ)20II .NFI;

wherein R is a member selected from the group consisting 0 methyl and hydrogen; wherein R is a member selected from the group consisting of lower alkyl and lower hydroxy alkyl, with sodium sand in an amount sufiicient to provide 1 mol of sodium for each hydroxyl group of the amino alcohol to be oxyalkylated, oxyalkylating the resulting amino-ONa compound with a compound containing at least one wherein R is a member selected from the group consisting of methyl and hydrogen; wherein R is a member selected from the group consisting of lower alkyl, lower hydroxyalkyl and a radical having the formula:

wherein R, is a member selected from the group consisting of the radicals:

wherein R; is a member selected from the group con sisting of hydrogen, phenyl, amino substituted phenyl, halo substituted phenyl, alkyl, hydroxyl substituted alkyl, halo substituted alkyl, alkenyl and phenyl substituted alkyl, wherein x is an integer ranging from 1 to 20 and y is an integer ranging from 1 to 20 comprises interacting an amino alcohol having the following general formula:

R: [R -C ((ll2) :Oll]

l lllz a R;2'(CHR4):OII

wherein R is a member selected from the group consisting of methyl and hydrogen; wherein R is a member selected from the group consisting of lower alkyl and lower hydroxy alkyl, with sodium methoxide in an amount sufficient to provide 1 mol of sodium for each hydroxyl group of the amino alcohol to be oxyalkylated,

1 1 oxyalkylating the resulting amino-ONa compound with a compound containing at least one o C C 0 il I l grouping selected from the group consisting of alkylene oxides, halo substituted alkylene oxides, phenyl substituted alkylene oxides, aminophenyl substituted alkylene oxides, halophenyl substituted alkylene oxides, and alkylene dioxides, at temperatures ranging from about 50 to about 100 C. and at pressures ranging from atmospheric to 20 p.s.i.g. to form an amino sodium-containing oxyalkylation product, subsequently treating the amino so- References Cited by the Examiner The following references, cited by the Examiner, are of record in the patented file of this patent or the original patent.

UNITED STATES PATENTS 2,782,240 2/1957 Hefner et 211. 2,871,266 1/1959 Riley. 2,944,984 7/1960 De Groote et 3].

CHARLES B. PARKER, Primary Examiner.

ROBERT V. HINES, Assistant Examiner. 

